US9761861B1 - Pulse plating of lithium material in electrochemical devices - Google Patents

Pulse plating of lithium material in electrochemical devices Download PDF

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US9761861B1
US9761861B1 US14/288,406 US201414288406A US9761861B1 US 9761861 B1 US9761861 B1 US 9761861B1 US 201414288406 A US201414288406 A US 201414288406A US 9761861 B1 US9761861 B1 US 9761861B1
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anode
region
current
electrolyte
polarity
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Timothy Holme
Marie Mayer
Ghyrn Loveness
Zhebo Chen
Rainer Fasching
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Quantumscape Corp
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0438Processes of manufacture in general by electrochemical processing
    • H01M4/045Electrochemical coating; Electrochemical impregnation
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18Electroplating using modulated, pulsed or reversing current
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • H01M10/0585Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1395Processes of manufacture of electrodes based on metals, Si or alloys
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/60Other road transportation technologies with climate change mitigation effect
    • Y02T10/70Energy storage systems for electromobility, e.g. batteries

Abstract

The present invention is directed to battery system and operation thereof. In an embodiment, lithium material is plated onto the anode region of a lithium secondary battery cell by a pulsed current. The pulse current may have both positive and negative polarity. One of the polarities causes lithium material to plate onto the anode region, and the opposite polarity causes lithium dendrites to be removed. There are other embodiments as well.

Description

CROSS-REFERENCES TO RELATED APPLICATIONS
This application claims priority to U.S. Provisional Patent Application No. 61/839,339, filed Jun. 25, 2013, entitled “PULSE PLATING OF LITHIUM MATERIAL IN ELECTROCHEMICAL DEVICES”, which is incorporated by reference herein for all purposes.
STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT
NOT APPLICABLE
REFERENCE TO A “SEQUENCE LISTING,” A TABLE, OR A COMPUTER PROGRAM LISTING APPENDIX SUBMITTED ON A COMPACT DISK
NOT APPLICABLE
BACKGROUND OF THE INVENTION
The present invention is directed to battery system and operation thereof.
In the recent years, with a shortage of fossil-fuel based energy resources and adverse environmental effects from the consumption of fossil fuels, both the public and private sectors have made substantial investments into developing clean technologies. An important aspect of clean technologies is energy storage, or simply battery systems. In the past, many battery types have been developed and used, with their respective advantages and disadvantages. For its chemical properties, including high charge density, lithium material has been used in various parts of a battery. For example, in a rechargeable lithium-ion battery, lithium ions move from negative electrode to the positive electrode (or cathode) during discharging process; lithium ions move from positive electrodes to negative electrode during charging process. Typically, the negative electrode (or anode) accommodates and stores lithium ions when the battery is charged. In conventional lithium battery systems, negative electrodes typically comprise materials, such as graphite and/or organic compounds that store migrating lithium ion material.
Unfortunately, existing anode materials and structures thereof are often inadequate. Therefore, it is desirable to have improved anode materials, structures, and processes thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a simplified diagram illustrating a battery cell having a lithiated anode according to an embodiment of the present invention.
FIG. 2 is a simplified diagram illustrating a battery cell in a charging mode according to an embodiment of the present invention.
FIGS. 3A and 3B are simplified diagrams illustrating a process of applying pulse current to a battery cell according to an embodiment of the present invention.
FIG. 4 is a simplified diagram illustrating formation of dendrite.
FIG. 5 is a simplified diagram illustrating lifetime of a battery cell operated with pulse current of about 15 uA.
FIG. 6 is a simplified diagram illustrating lifetime of a battery cell operated with different pulse currents.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to battery system and operation thereof. In an embodiment, lithium material is plated onto the anode region of a lithium secondary battery cell by a pulsed current. The pulse current may have both positive and negative polarity. One of the polarities causes lithium material to plate onto the anode region, and the opposite polarity causes lithium dendrites to be removed. There are other embodiments as well.
As described above, lithium ions move through electrolyte and between positive and negative electrodes upon charging and discharging process. Typically, the anode region of a lithium battery cell comprises material such as graphite to store lithium ions when the battery is charged. According to embodiments of the present invention, lithium ions are plated onto the current collector at the side of the negative electrode. FIG. 1 is a simplified diagram illustrating a battery cell having a lithiated anode according to an embodiment of the present invention. This diagram is merely an example, which should not unduly limit the scope of the claims. One of ordinary skill in the art would recognize many variations, alternatives, and modifications.
The following description is presented to enable one of ordinary skill in the art to make and use the invention and to incorporate it in the context of particular applications. Various modifications, as well as a variety of uses in different applications will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to a wide range of embodiments. Thus, the present invention is not intended to be limited to the embodiments presented, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
In the following detailed description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. However, it will be apparent to one skilled in the art that the present invention may be practiced without necessarily being limited to these specific details. In other instances, well-known structures and devices are shown in block diagram form, rather than in detail, in order to avoid obscuring the present invention.
The reader's attention is directed to all papers and documents which are filed concurrently with this specification and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference. All the features disclosed in this specification, (including any accompanying claims, abstract, and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
Furthermore, any element in a claim that does not explicitly state “means for” performing a specified function, or “step for” performing a specific function, is not to be interpreted as a “means” or “step” clause as specified in 35 U.S.C. Section 112, Paragraph 6. In particular, the use of “step of” or “act of” in the Claims herein is not intended to invoke the provisions of 35 U.S.C. 112, Paragraph 6.
Please note, if used, the labels left, right, front, back, top, bottom, forward, reverse, clockwise and counter clockwise have been used for convenience purposes only and are not intended to imply any particular fixed direction. Instead, they are used to reflect relative locations and/or directions between various portions of an object.
FIG. 1 is a simplified diagram illustrating a battery cell having a lithiated anode according to an embodiment of the present invention. This diagram is merely an example, which should not unduly limit the scope of the claims. One of ordinary skill in the art would recognize many variations, alternatives, and modifications. As shown in FIG. 1, a battery cell 100 includes a cathode current collector 101, a cathode region 102, an electrolyte region 103, an anode region 104, and an anode current collector 105. The cathode current collector 101 is electrically conductive. In various embodiments, the cathode current collector 101 comprises metal material, such as aluminum, carbon-coated aluminum, nickel, copper, lithium, polymer material with metal plating, and/or other types of material. The cathode region 102 as shown interfaces with the cathode current collector 101. For example, the cathode region 102 is lithiated and can accommodate lithium ions when the battery cell 100 is discharged. The cathode region is preferably fabricated in the lithiated, (i.e. discharged state), since it will be less reactive in that state. Alternatively, the cathode could be for a lithium-air (Li—O2) cell or a lithium sulfur (Li—S) cell. For example, Li—O2 and Li—S refers to elemental lithium, oxygen, and sulfur. Depending on the implementation, materials in their elemental forms can be easier to process than compound form.
The cathode region 102 is coupled to the electrolyte 103. According to embodiments of the present invention, the electrolyte 103 is a solid electrolyte material with a high level of ionic conductivity. For example, the ionic conductivity of the electrolyte can be at least 10−7 S/cm. The electrolyte may be a ceramic material. Depending on the implementation, electrolyte may also be a polymer, ionic liquid, gel, or liquid electrolyte. The electrolyte may comprise additives such as CsPF6 or HF that inhibit dendrite formation. Exemplary ceramic electrolyte materials include, but are not limited, to LiPON, LiAlF4, Li3N, Li β″ alumina, (LiLa)TiO3, Li9AlSiO8, garnets such as Li7La3Zr2O12, antiperovskites such as Li3ClO, oxide glasses, Lisicon structures such as Li14Zn(GeO4)4, Li3.6Si0.6P0.4O4, sulfide glasses, oxysulfide glasses, sulfide or oxysulfide glass ceramics, sulfide crystals such as Li3PS4, Li10XP2S12 (X=Si, Ge, Sn and combinations thereof), Li7P3S11, or Li3.25Ge0.25P0.75S4. The electrolyte may be comprised of two or more layers of lithium ion conducting materials. Interfacing with the other side of the electrolyte 103 is an anode region 104. In various embodiments, the anode region 104 is formed by applying a pulsed current. More specifically, during the charging process of the battery cell 100, lithium ions migrate from cathode region 102 through the electrolyte 103 and plate onto the anode region 104.
The anode current collector 105 provides electrical contacts to the anode region 104. For example, the anode current collector material interfacing the anode region 104 is metal, and the anode current collector interface allows lithium ion to plate onto the metal material during the charging process. As a part of the battery, the anode current collector is a metal material that does not alloy with lithium according to a specific embodiment. Depending on the implementation, the anode current collector may be a metal or a polymer coated with a non-alloying material. As an example, suitable non-alloying materials include titanium nitride, tungsten, molybdenum, copper, nickel, iron or stainless steel. The anode current collector may optionally include a layer of a metal that enhances plating uniformity such as indium, aluminum, or magnesium. The anode current collector may also optionally include a layer that improves adhesion between current collector and electrolyte during lithium stripping (battery discharge). The anode current collector may be a lithium foil or a deposited lithium layer. As an example, battery structures are described in U.S. Provisional Patent Application No. 61/814,821, entitled “NANOSTRUCTURED MATERIALS FOR ELECTROCHEMICAL CONVERSION REACTIONS”, filed 23 Apr. 2013, which is incorporated by reference herein for all purposes.
According to various embodiments, the anode region 104 is formed in situ with regard to the battery cell. More specifically, the battery cell 100, before its first operation, does not have the anode region 104; the electrolyte 103 directly interfaces with the anode current collector 105. When the battery cell 101 is charged for the first time (i.e., applying pulse current between the cathode and anode current collector), the anode region 104 is formed by lithium ions plating onto the anode current collector 105. When the battery cell 101 is discharged, the lithium ions at the anode region migrate to the cathode region 102 through the electrolyte 103. The detailed process of forming the anode region with pulsed current is described below.
FIG. 2 is a simplified diagram illustrating a battery cell in a charging mode according to an embodiment of the present invention. This diagram is merely an example, which should not unduly limit the scope of the claims. One of ordinary skill in the art would recognize many variations, alternatives, and modifications. In FIG. 2, a battery cell 200 includes a cathode current collector 201, a cathode region 202, an electrolyte region 203, an anode region 204, and an anode current collector 205. The cathode region is preferably fabricated in a substantially lithiated, i.e. discharged state. The anode region is preferably fabricated in a substantially delithiated state and may be lithiated upon the first charge of the battery. The anode region 204, positioned between the electrolyte 203 and the anode current collector 205, expands during the charging process, as lithium ions migrate into the anode region. For example, the electrolyte 203 is flexible and thus accommodates the volume expansion of the anode region 204. In various embodiments, the electrolyte 203 comprises solid electrolyte material and has a thickness of less than 10 microns. Depending on the implementation, the electrolyte material can also have a thickness of less than 50 microns. The electrolyte interfacing with the lithium metal anode is characterized by a permittivity ε and a conductivity σ, and the majority of current pulses are of a duration longer than εε0/σ, where ε0 is the permittivity of free space. The permittivity may be measured by means known to those skilled in the art, for example by measuring the high frequency capacitance of the sample and extracting the permittivity from the formula C=εε0A/d, where A is the area of the electrolyte and d is the thickness of the electrolyte. The conductivity may be measured by means known to those skilled in the art, for example by electrochemical impedance spectroscopy or by DC galvanostatic plating at a fixed current of I and measuring the potential V, and calculating σ=(I*d)/(V*A). The characteristic time constant of the electrolyte interface is t=RC, where R is the resistance and C is the capacitance. This time constant may also be expressed t=RC=(d/Aσ)*(εε0A/d)=εε0/σ and gives the characteristic time that ions move in the electrolyte. It is to be understood that pulses are preferably of a duration longer than this time constant to allow ions sufficient time to move in response to the applied pulse duration. For electrical performance and reliability, it is desirable for the anode region 204 to be substantially uniform. Undesirably, during the charging process, dendrites form near the anode region 204. For example, FIG. 2 illustrates that dendrite region 206 formed between the anode region 204 and the electrolyte 203. It is to be understood that the dendrites may form in other regions near the anode region 204 and in the electrolyte as well. It is to be understood that lithium plating may be non-uniform in several different morphologies. For example, it may be dendrite-like and/or it may be “mossy”, or high surface area. For example, the non-uniform plating of lithium material may accumulate and worsen over time, thereby degrading battery performance and potentially leading to device failure.
In general, lithium dendriting is undesirable, as it can be a cause of battery failure. More specifically, dendrite formation may create a short circuit between the cathode region 202 and the anode region 204, and such short may constitute a catastrophic failure. Lithium dendrites sometimes cause problems by creating a thermal runaway that leads to safety events. To solve or otherwise alleviate the dendrite formation problem, conventional battery cells typically use barrier structures that employ oversize graphite (and/or other material) to prevent lithium plating and dendrite formation. Unfortunately, anodes typically have low energy density due to the graphitic anode rather than lithium metal anode and further require exotic chemical additives and formation cycles to form a solid electrolyte interface (SEI). Thus it is to be appreciated that embodiments of the present invention provide techniques of charging the lithiated anode region using pulsed current, which also removes lithium dendrites. It is to be appreciated that by using pulse current to charge battery cells according to embodiments of the present invention, dendriting problems can be alleviated or eliminated inexpensively, without lowering the energy density of battery cells. It is to be appreciated that the pulsed plating may be applied as part of the formation cycle(s) to condition the cell and create a lithium metal anode in situ. This technique may be applied to lithium metal anodes and to other anodes where dendriting is to be avoided, for example, Sn, Si, Ge, graphite, and alloys of these compounds.
FIG. 3A is a simplified diagram illustrating a process of applying pulsed current to a battery cell according to an embodiment of the present invention. This diagram is merely an example, which should not unduly limit the scope of the claims. One of ordinary skill in the art would recognize many variations, alternatives, and modifications. The waveform shown in FIG. 3 is a current waveform for galvanostatic pulse (and/or reverse-pulse) plating of lithium material onto the anode (or anode current collector). On the waveform, If is the forward (plating) current, Ir is the reverse (stripping) current, tf is the time during which the forward current is applied, and tr is the time during which the reverse current is applied. When If is applied to the cathode and anode current collectors over tf, lithium ions move from cathode to anode and plate onto the anode region and/or the anode current collector. The magnitudes of If and the duration tf are specifically calibrated to promote lithium plating uniformity and avoid dendrite formation. The amount of lithium plating is a function If and tf, or total charge applied during tf. In various embodiments, the pulse current is characterized by a net current density of 0.1 mA/cm2 to 50 mA/cm2. Although the schematic in FIG. 3 presents substantially square waveforms for the plating and stripping current, other waveforms may be used as well. For example, the waveform may be sawtooth, rounded as in FIG. 3B, or arbitrary.
During tr, current Ir, which is opposite in polarity relative to the If, is applied to the battery cell. It is to be appreciated that while If and Ir are respectively shown as negative and positive, the polarities are relative to the battery cell terminals; it is to be understood that If is meant to represent a polarity for lithium plating, and Ir for lithium stripping. In certain embodiments, the magnitude of Ir is substantially zero. A non-zero magnitude of Ir is applied for the purpose of removing dendrite that may have formed during tf. More specifically, during tr, lithium is preferentially stripped from the tip of dendrites due to the field concentration around dendrite tips (the very effect that causes dendritic growth). FIG. 4 is a simplified diagram illustrating formation of dendrite. As shown in FIG. 4, electric field concentrates at dendrite tips, which causes a “mossy” dendritic growth. Now referring back to FIG. 3; the total amount of lithium material to be removed is less than the total amount of lithium that has plated.
According to various embodiments, both tf and tr, the forward and reverse time, should be longer than the RC time constant of Li plating at the interface between the lithium and electrolyte. For example, tf and tr duration are on the order of 1 ms or greater.
The plating efficiency is the forward charge plated (Qplate=∫Iplatedtplate) less the charge stripped (Qstrip=∫Istripdtstrip) divided by total charge plated, as expressed in the equation below:
η = Q plate - Q strip Q plate
The plating efficiency η is typically greater than 50%. However, a “clean-up” cycle may be performed in which the plating efficiency is less than 50%, and may be negative. For the pulsed current, the average net current is defined by the equation below:
I avg , net = I plate d t - I strip d t t tot
To increase the efficiency, the greatest ratio of Qplate/Qstrip is desired. In the limit that Qstrip→0, only forward plating is performed, which may result in dendrites. It is be appreciated that there is an optimum range of the 4 parameters, as explained below, that leads to effective suppression of dendrites while retaining high efficiency. One example setting is to use a substantially square current waveform with Iplate=Istrip=0.1 mA/cm2 and tf=25 ms, tr=5 ms. Another example is to use a substantially square current waveform with Iplate=Istrip/x where 1≦x≦10 and tf=tr*y where 1.1x≦y≦5x. Another example is to use an RC-shaped waveform with similar ranges for the times and maximum current magnitudes. As tplate and tstrip increase at a fixed ratio of tplate/tstrip, it is to be appreciated that the pulsed plating effectively approaches DC plating. Therefore, many of the benefits of pulsed plating are derived at shorter plating and stripping times, for example tplate<60 s, or tplate<15 s or tplate<2 s or tplate<100 ms or tplate<50 ms.
The stripping current is preferably large enough to be in the IR-limited regime as opposed to the activation-limited regime. This may be determined by a Tafel plot of the overpotential versus the logarithm of the current density. The activation-limited regime at low current density will appear linear on this plot. A deviation from linearity often signifies a transition into the IR-limited regime. It is to be appreciated that stripping in the IR limited regime will enhance the selectivity of stripping from a dendrite tip since the ohmic (IR) drop will be lower for current traveling to a protrusion (dendrite)) than for current traversing the entire electrolyte to the evenly plated material.
It is to be appreciated that the pulsed current can have multiple cycles, even though FIG. 3 only one cycle that includes tf and tr. It is to be understood that to fully charge a battery cell, a large number of cycles may be required. Depending on the implementation, pulse magnitude and duration may be variable too. In the case where the anode is fully discharged (contains no lithium), pulse plating may be especially useful to nucleate a good smooth layer. Lithium plating is known to occur with some overpotential, therefore it will nucleate in localized areas and further plating will occur preferentially on top of those areas resulting in an increasing roughness. Pulse and pulse/reverse-pulse plating may alleviate this issue.
The pulse current illustrated in FIG. 3 can be used for forming anode region and/or charging a battery cell. In a specific embodiment, a battery cell as manufactured does not have an anode region; lithium ions are stored at the cathode region, and the anode current collector interfaces directly with the electrolyte. Upon first charging of the battery cell, with pulsed current illustrated in FIG. 3, the lithium ions at the cathode region migrate across the electrolyte to form an anode region between the anode current collector and the electrolyte. With the anode region formed, the future charging processes, which can be performed with pulsed current, redeposit lithium ions to the anode region.
It is to be appreciated that the charging techniques with pulsed current according to embodiments of the present invention provide numerous benefits. FIG. 5 presents experimental data comparing the lifetime of a battery cell operated with DC plating versus a pulse current of about Ir=If=15 uA over an area of 0.28 cm2. The results show a statistically significant difference that the pulse plating prolongs lifetime to failure of the cell. At 15 uA, the sample battery cell that underwent pulsed plating with square pulses with tf=125 ms and tr=50 ms had a statistically significant longer lifetime. The test platform used was an iron back electrode contact, LiPON solid state electrolyte of 400 nm thickness with a pressed Li foil top electrode that served as the Li source. The ratio of the pulse/strip current was held to 2.5 for all cases. Compared to charging with continuous DC current, charging with charged current provide much better reliability and lifetime.
FIG. 6 presents experimental data illustrating lifetime of a battery cell operated with different pulse currents. Using a test platform with iron back contact of area 0.28 cm2 and LiPON solid-state electrolyte of about 400 nm thickness with a pressed lithium foil as lithium source and top electrode, current was run in DC or pulsed modes until failure was measured by a voltage drop towards 0V from the plating (stripping) voltage. The plated charge at cell failure was calculated from Qnet=Qplate−Qstrip. From the top to bottom, the circles represent pulsed current of 5, 15, and 30 uA. An increase in the plating current increases the time to failure. This result is consistent with DC plating results in FIG. 5.
A statistical analysis of failure in cells with geometry as described above is summarized in the following table:
TABLE 1
Plated charge [mC] at cell failure Lowest quartile (25%) Lowest 10%
DC plating 18.6 1.5
Pulse plating 53.6 15
As shown in table 1 above, samples have a much higher reliability (measured in plated charge at cell failure) for pulse plating, than DC plating. For the lowest 10% where the earliest failures occur, pulse plating is as much as 10 times (15 mC v. 1.5 mC) more reliable than DC plating. This is an important reliability metric for a product since it is desirable that the earliest onset of failures occurs at as late a time as possible. At the lowest quartile, pulse plating can provide lifetime of about 3 times (53.6 mC v. 18.6 mC) longer than DC plating. By having much higher reliability rating at lowest quartile and lowest decile, devices with pulse plating can last longer and be more safe than the device with DC plating.
It is to be understood that while above description provides exemplary parameters for electrochemical device structures and operations thereof, actual parameters depend on specific implementations, and should not unduly limit the claims. For example, a large number of battery cells may be stacked in parallel, and as a result a large current is needed to charge these battery cells, cause lithium material to plate the anode region, and/or remove the lithium dendrite.
According to certain embodiments, battery cells are managed by a battery management system (BMS), which stores information related to the properties of the battery cells. Among other things, state of charge information and parameters for charging with pulsed current are stored in the BMS. When the battery cells are to be charged, parameters for the pulsed current are determined based on the information stored in the BMS. In a specific embodiment, the BMS comprises a charging mechanism that converts constant DC current received from a charging station to a pulsed current suitable for charging the battery cells.
According to an embodiment, a BMS includes sensor that monitors the state of charge for the battery cells. The anode regions of the battery cells are characterized by variable thicknesses associated with the number of life cycles of the battery device. For example, once a battery device cycles many times, the thickness of the anode region(s) increases as result of lithium material permanently deposited at the anode regions. The BMS system, by monitoring the thickness of the anode region, can determine charging characteristics for the battery device.
In certain embodiments, charging with a pulsed current is performed by a charging device. For example, battery cells together form a battery pack, which essentially powers the drivetrain of an electric vehicle (EV). To charge, the battery pack is plugged into a charging device, which can be a commercial charging station or a home charging setup. The charging device is configured to generate a pulsed current to charge the battery pack. In a specific embodiment, the charging device obtains information related to the characteristics of the battery pack and/or the battery cells (state of charge, state of health, etc.), and various parameters (e.g., pulse magnitude, duration, plating efficiency, etc.) of the pulsed current are determined accordingly. In addition to generating a pulsed current, the charging device may additionally be adapted to perform other tasks, such as performing AC/DC power conversion, regulating power supply, and others.
Alternately, a battery charging station may be configured so as to deliver pulsed current for charging of electrical applications. Electric vehicle charging requires high power delivery, thus the charging station will need particular high power switching electronics to be able to switch high currents. For example, level 1 charging requires 120 VAC at 16 A, level 2 charging requires 208 VAC and 12-80 A (roughly 2-20 kW), and level 3 requires 300-600 VDC and up to 400 A (up to 240 kW).
While the above is a full description of the specific embodiments, various modifications, alternative constructions and equivalents may be used. Therefore, the above description and illustrations should not be taken as limiting the scope of the present invention which is defined by the appended claims.

Claims (20)

What is claimed is:
1. A method for forming a lithium metal anode in an electrochemical device, the method comprising:
providing a cathode, the cathode having a positive current collector;
providing a lithium conducting electrolyte region having a top surface and a bottom surface, the top surface interfacing a lithiated cathode;
providing a negative current collector interfacing the bottom surface of the electrolyte region; and
supplying a plurality of current pulses, the plurality of current pulses comprising a first pulse and a second pulse, the first pulse causing a formation of a layer of lithium metal anode positioned between the negative current collector and the bottom surface, the first pulse being characterized by a first amount of charge and first polarity during a first duration, the second pulse being characterized by a second amount of charge and second polarity during a second duration, the first amount of charge being greater than the second amount of charge.
2. The method of claim 1, wherein:
the layer of lithium metal anode comprises a non-uniform region;
the first polarity is opposite from the second polarity;
the second pulse causes a removal of a portion of the non-uniform region during the second duration.
3. The method of claim 1 wherein the layer of lithium metal anode is formed in-situ.
4. The method of claim 1 wherein the second magnitude is substantially zero.
5. The method of claim 1 wherein the first polarity and the second polarity are opposite.
6. The method of claim 1 wherein the electrolyte region is characterized by a thickness of less than 10 microns.
7. The method of claim 1 wherein the electrolyte region is characterized by a thickness of less than 50 microns.
8. The method of claim 1 wherein the plurality of current pulses is characterized by an average net current density of 0.1 mA/cm2 to 50 mA/cm2.
9. The method of claim 1 wherein the plurality of current pulses comprises a pulse of the first polarity to charge the device interspersed by rest periods.
10. The method of claim 1 wherein the plurality of current comprises a first plurality of pulses in the first polarity to charge the device interspersed by second plurality of pulses in a second polarity, the second polarity being a reverse polarity relative to the first polarity.
11. The method of claim 1 being characterized by a plating efficiency η>50%, where the plating efficiency η is defined by the equation η=(qplate−qstrip)/(qplate).
12. The method of claim 1, wherein the lithium conducting electrolyte region interfaces the lithium metal anode at the bottom surface, the lithium metal anode is characterized by a permittivity ε and a conductivity σ, and the majority of current pulses are of a duration longer than εε0/σ, wherein ε0 is the permittivity of free space.
13. The method of claim 12 wherein the electrolyte comprises a polymer.
14. The method of claim 1 wherein the electrolyte comprises a solid ceramic.
15. A method for operating a lithium metal anode electrochemical device,
wherein the electrochemical device comprises a cathode current collector, an anode current collector, a solid electrolyte having a thickness of at least 400 nm positioned between the cathode current collector and the anode current collector, and an anode region defined between the anode current collector and the solid electrolyte having a thickness of at least 400 nm, the method comprising:
applying a plurality of current pulses between the cathode current collector and the anode current collector; and
causing lithium material within the electrochemical device to plate onto the anode region in response to the first pulse of current.
16. The method of claim 15 wherein a net charge transfer of the plurality of current pulses is greater than zero.
17. The method of claim 15 wherein the plurality of current pulses comprises pulses of current in a polarity to charge the device interspersed by rest periods.
18. The method of claim 15 wherein a majority of the plurality of current pulses is of a duration longer than a characteristic relaxation time of a double-layer at the interface of the lithium metal anode.
19. The method of claim 15 further comprising removing a dendrite layer formed near the anode region.
20. A method for removing a dendrite from an electrochemical device, wherein
the electrochemical device comprises a cathode region, an anode region, an electrolyte region positioned between the cathode region and the anode region, and a lithiated dendrite layer formed between the anode region and the electrolyte region, the method comprising:
supplying a plurality of current pulses between the cathode region and the anode region to remove at least a portion of the lithiated dendrite.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200127285A1 (en) * 2018-10-19 2020-04-23 GM Global Technology Operations LLC Negative electrode for lithium secondary battery and method of manufacturing

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA3040251A1 (en) 2015-12-09 2017-06-15 Nanoscale Components, Inc. Methods for alkaliating roll anodes
CN108550907B (en) * 2018-06-05 2020-08-21 北京卫蓝新能源科技有限公司 In-situ composite solid electrolyte and application thereof, all-solid-state battery and preparation method thereof
US11024877B2 (en) 2018-12-04 2021-06-01 TeraWatt Technology Inc. Anode-free solid-state battery cells with anti-dendrite and interface adhesion controlled functional layers
US20200365903A1 (en) * 2019-05-16 2020-11-19 TeraWatt Technology Inc. Volume-Expansion Accommodable Anode-Free Solid-State Battery
US20210036363A1 (en) * 2019-07-29 2021-02-04 TeraWatt Technology Inc. Phase-change electrolyte separator for a solid-state battery
US20210104785A1 (en) * 2019-10-06 2021-04-08 RFNAV Inc. Apparatuses and Methods for Acoustic and Current Manipulation of Anode Interface Deposits in Lithium Anode Batteries and other Battery Systems

Family Cites Families (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4288505A (en) 1980-10-24 1981-09-08 Ray-O-Vac Corporation High energy density solid state cell
US5436548A (en) 1992-11-25 1995-07-25 Motorola, Inc. Battery charging and discharging system and corresponding method
US7247408B2 (en) 1999-11-23 2007-07-24 Sion Power Corporation Lithium anodes for electrochemical cells
US6733924B1 (en) 1999-11-23 2004-05-11 Moltech Corporation Lithium anodes for electrochemical cells
JP4174816B2 (en) 2001-02-28 2008-11-05 住友電気工業株式会社 Inorganic solid electrolyte and lithium battery member
US6680145B2 (en) 2001-08-07 2004-01-20 3M Innovative Properties Company Lithium-ion batteries
US7041239B2 (en) 2003-04-03 2006-05-09 Valence Technology, Inc. Electrodes comprising mixed active particles
JP4813767B2 (en) 2004-02-12 2011-11-09 公立大学法人大阪府立大学 Lithium ion conductive sulfide crystallized glass and method for producing the same
KR100659851B1 (en) 2005-04-27 2006-12-19 삼성에스디아이 주식회사 Lithium secondary battery
JP4834442B2 (en) 2006-03-31 2011-12-14 出光興産株式会社 Solid electrolyte, method for producing the same, and all-solid-state secondary battery
EP2093824A4 (en) 2006-11-14 2014-08-06 Ngk Insulators Ltd Solid electrolyte structure for all-solid-state battery, all-solid-state battery, and their production methods
CN102124601B (en) 2008-06-16 2014-02-12 波利普拉斯电池有限公司 Aqueous lithium/air battery cells
US20160111715A9 (en) 2008-06-20 2016-04-21 Toyota Motor Engineering & Manufacturing North America, Inc. Electrode material with core-shell structure
JP2010272494A (en) 2008-08-18 2010-12-02 Sumitomo Electric Ind Ltd Nonaqueous electrolyte secondary battery and method for producing the same
JP5558482B2 (en) 2008-11-20 2014-07-23 エルジー・ケム・リミテッド Secondary battery electrode active material and method for producing the same
WO2010081170A1 (en) 2009-01-12 2010-07-15 Rutgers, The State University Polyhydrogen fluoride based battery
JP5287739B2 (en) 2009-05-01 2013-09-11 トヨタ自動車株式会社 Solid electrolyte material
JP5605722B2 (en) 2009-09-29 2014-10-15 エルジー・ケム・リミテッド Separator manufacturing method, separator formed therefrom, and manufacturing method of electrochemical device including the same
US8697292B2 (en) 2010-03-26 2014-04-15 Tokyo Institute Of Technology Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material
US8951668B2 (en) 2010-11-19 2015-02-10 Rutgers, The State University Of New Jersey Iron oxyfluoride electrodes for electrochemical energy storage
JP5002824B1 (en) 2011-03-02 2012-08-15 五鈴精工硝子株式会社 Negative electrode material for lithium secondary battery and production method thereof, and negative electrode for lithium secondary battery and lithium secondary battery
CN103718337B (en) * 2011-06-17 2017-09-26 赛昂能源有限公司 Electroplating technology for electrode
JP5780880B2 (en) 2011-08-09 2015-09-16 日東電工株式会社 Lithium secondary battery and negative electrode thereof
CN102983378A (en) 2011-09-07 2013-03-20 徐辛 Method and device for carrying out charging and discharging upon storage batteries by using ultrasonic waves
JP5888610B2 (en) 2011-12-22 2016-03-22 国立大学法人東京工業大学 Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material
JP5880581B2 (en) 2012-02-06 2016-03-09 トヨタ自動車株式会社 Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material
JP5888609B2 (en) 2012-02-06 2016-03-22 国立大学法人東京工業大学 Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material
US20150056520A1 (en) * 2012-03-01 2015-02-26 Johnson Ip Holding, Llc Impregnated sintered solid state composite electrode, solid state battery, and methods of preparation
CN110416478A (en) * 2012-03-01 2019-11-05 约翰逊Ip控股有限责任公司 Solid union barrier film, its manufacturing method and solid state rechargeable lithium battery
CN103579707B (en) 2012-07-20 2016-01-06 纳米新能源(唐山)有限责任公司 Self-charging lithium ion battery
US9692039B2 (en) 2012-07-24 2017-06-27 Quantumscape Corporation Nanostructured materials for electrochemical conversion reactions
US9048497B2 (en) 2012-10-05 2015-06-02 Rutgers, The State University Of New Jersey Metal fluoride compositions for self formed batteries
US9166253B2 (en) 2012-12-06 2015-10-20 Samsung Electronics Co., Ltd. Solid-state battery
US9786905B2 (en) 2013-03-13 2017-10-10 Quantumscape Corporation Iron, fluorine, sulfur compounds for battery cell cathodes
JP6668231B2 (en) 2013-05-15 2020-03-18 クアンタムスケイプ コーポレイション Solid catholyte or electrolyte for batteries
US9181408B2 (en) 2013-07-06 2015-11-10 Nike, Inc. Method of forming a cured elastomer and golf balls
FR3010832B1 (en) 2013-09-16 2017-12-15 Commissariat Energie Atomique PROCESS FOR PRODUCING LITHIUM MICROBATTERIUM
EP3055269B1 (en) 2013-10-07 2020-09-09 QuantumScape Corporation Garnet materials for li secondary batteries
KR20160125354A (en) 2014-02-25 2016-10-31 콴텀스케이프 코포레이션 Hybrid electrodes with both intercalation and conversion materials
TW201628249A (en) 2014-08-28 2016-08-01 應用材料股份有限公司 Electrochemical device stacks including interlayers for reducing interfacial resistance and over-potential
US10205155B2 (en) 2014-10-14 2019-02-12 Quantumscape Corporation High surface area anode with volume expansion features
US10116003B2 (en) 2015-02-03 2018-10-30 Quantumscape Corporation Metal sulfide anolytes for electrochemical cells
US9960458B2 (en) 2015-06-23 2018-05-01 Quantumscape Corporation Battery systems having multiple independently controlled sets of battery cells
WO2017065035A1 (en) 2015-10-15 2017-04-20 日本碍子株式会社 All-solid-state lithium battery
US9966630B2 (en) 2016-01-27 2018-05-08 Quantumscape Corporation Annealed garnet electrolyte separators
US20200020990A1 (en) 2017-03-10 2020-01-16 Quantumscape Corporation Metal negative electrode ultrasonic charging
CN113056838A (en) 2018-10-02 2021-06-29 昆腾斯科普电池公司 Method for producing and using electrochemical cells with an interlayer

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
Chandrasekar, M.S., et al., "Pulse and pulse reverse plating-Conceptual, advantages and applications," Electrochimica Acta, 2008, vol. 53, pp. 3313-3322.
Chandrasekar, M.S., et al., "Pulse and pulse reverse plating—Conceptual, advantages and applications," Electrochimica Acta, 2008, vol. 53, pp. 3313-3322.
Dini, Jack W., et al., "Electrodeposition of Copper," Chapter 2, Modern Electroplating, Fifth Edition, 2010, pp. 33-78.
Kim, Hansung, et al., "Preparation of PEM fuel cell electrodes using pulse electrodeposition," Journal of Power Sources, 2004, vol. 138, pp. 14-24.
Mayers, Matthew Z., "Suppression of dendrite formation via pulse charging in rechargeable lithium batteries," The Journal of Physical Chemistry, 2012, vol. 116, pp. 26214-26221.
Mayers, Matthew Z., "Suppression of dendrite formation via pulse charging in rechargeable lithium metal batteries," The Journal of Physical Chemistry, 2012, vol. 116, pp. 26214-26221. *
U.S. Appl. No. 61/814,821, filed Apr. 23, 2013 entitled, "Nanostructured Materials for Electrochemical Conversion Reactions," 30 pages.
Ye, Feng, et al., "Shape-controlled fabrication of platinum electrocatalyst by pulse electrodeposition," Electrochemistry Communications, 2008, vol. 10, pp. 476-479.
Zoval, J. V., et al., "Electrochemical preparation of platinum nanocrystallites with size selectivity on basal plane oriented graphite surfaces," J. Phys. Chem. B, 1998, vol. 102, pp. 1166-1175.

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200127285A1 (en) * 2018-10-19 2020-04-23 GM Global Technology Operations LLC Negative electrode for lithium secondary battery and method of manufacturing
US10938028B2 (en) * 2018-10-19 2021-03-02 GM Global Technology Operations LLC Negative electrode for lithium secondary battery and method of manufacturing

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